CN110639533B - Copper/modified bismuth vanadate composite photocatalytic material, preparation method and application - Google Patents
Copper/modified bismuth vanadate composite photocatalytic material, preparation method and application Download PDFInfo
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- CN110639533B CN110639533B CN201911005877.9A CN201911005877A CN110639533B CN 110639533 B CN110639533 B CN 110639533B CN 201911005877 A CN201911005877 A CN 201911005877A CN 110639533 B CN110639533 B CN 110639533B
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- -1 Copper/modified bismuth vanadate Chemical class 0.000 title claims abstract description 89
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 133
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 66
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 55
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 51
- 239000010949 copper Substances 0.000 claims abstract description 51
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 44
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 73
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000012153 distilled water Substances 0.000 claims description 23
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 20
- 229910052802 copper Inorganic materials 0.000 abstract description 19
- 239000011941 photocatalyst Substances 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- 239000011218 binary composite Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 22
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 20
- 229940043267 rhodamine b Drugs 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000032900 absorption of visible light Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- B01J35/39—
-
- B01J35/393—
-
- B01J35/394—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a preparation method of a copper/modified bismuth vanadate composite photocatalytic material, which comprises the following steps: s1, preparing bismuth vanadate containing silicon dioxide; s2, preparing modified bismuth vanadate; s3, preparing copper/modified bismuth vanadate; by means of SiO2For BiVO4Modifying to prepare the modified BiVO with uniformly dispersed particle size4The micro-nano particles are loaded with nano-particle copper on the basis, so that the photocatalytic performance of the composite photocatalytic material is effectively improved; the binary composite photocatalyst Cu/modified BiVO of the invention4Under the irradiation of visible light, the performance of photocatalytic degradation of organic pollutants is greatly improved. Modified BiVO4BiVO (BiVO) with smaller particle size and rougher surface and modified Cu nanoparticles4The uniformity of the upper load is better, and the bonding strength is higher; effectively promote BiVO4The photocatalytic performance of (a).
Description
Technical Field
The invention belongs to the technical field of inorganic photocatalyst materials, and particularly relates to a copper/modified bismuth vanadate composite photocatalytic material, a preparation method and application.
Background
Photocatalytic degradation of organic pollutants is considered to be one of the most promising strategies for creating a clean and pollution-free environment for humans in modern society. The success of photocatalytic degradation depends largely on the proper choice of the photocatalyst material, bismuth vanadate (BiVO)4) Considerable attention has been paid to the high stability, narrow band gap, non-toxicity and advanced visible light utilization. BiVO4Is a typical ternary semiconductor having a layered structure with three crystal forms, monoclinic scheelite, tetragonal scheelite and tetragonal-like zircon, in which phase transitions can occur between these phases under different thermal conditions. It is reported that monoclinic BiVO having a band gap of 2.4eV4Can absorb solar spectrum in blue light region of about 520nm, thereby leading to BiVO of monoclinic scheelite structure4Can exhibit significantly better visible light driven photocatalytic performance than other crystal structures.
BiVO4Although the photocatalyst has good photocatalytic activity, the photocatalyst also has some disadvantages, such as weak surface adsorption capacity, easy recombination of photo-generated electrons and holes, and the like. In order to increase BiVO4The photocatalytic performance of the material, BiVO of researchers at home and abroad4Modification of photocatalysts has been extensively studied. To date, BiVO has been demonstrated with many metals, such as Ag, Co, Ni, Cu and other metals doping4Is effective in enhancing its photocatalytic activity. Thus, BiVO doped with metal ions or metal oxides4Are considered to be a viable route to enhance the photodegradation of organic pollutants.
Therefore, in order to further enrich various photocatalytic materials with visible light catalytic efficiency, the invention takes silicon dioxide as a modifier to prepare modified BiVO by calcining at high temperature solid phase aiming at the problem of weak catalytic activity of bismuth vanadate4. Meanwhile, the Cu nano particles have the advantages of plasma property superior to other transition metals, excellent electron accepting and shuttling capacity, band edge expansion capacity, antibacterial property and cost benefit. Further using reductionThe process loads Cu nano particles on BiVO4The Cu/modified BiVO is prepared4The binary photocatalyst promotes the migration capability of a photon-generated carrier to the surface of the catalyst by utilizing the characteristics of the metal Cu nano particles, thereby promoting BiVO4The photocatalytic efficiency of (c).
Disclosure of Invention
The invention aims to provide a copper/modified bismuth vanadate composite photocatalytic material, a preparation method and application, which are used for solving the problem that bismuth vanadate is weak in catalytic activity as a photodegradation catalyst, and the problems of low Cu nanoparticle loading capacity, poor uniformity and low bonding strength caused by the fact that Cu nanoparticles are loaded on bismuth vanadate only.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a copper/modified bismuth vanadate composite photocatalytic material comprises the following steps:
s1 preparation of bismuth vanadate containing silicon dioxide
s11, dissolving a bismuth source in an organic solvent, and stirring to obtain a solution A;
s12, mixing a vanadium source, ascorbic acid, a nitric acid solution and distilled water in a container, heating and cooling to room temperature to obtain a solution B;
s13, adding the solution A into the solution B under the stirring condition, and obtaining BiVO after reaction4Solution, then soaking silica in said BiVO4Obtaining a mixture in the solution; calcining the mixture at high temperature to obtain bismuth vanadate containing silicon dioxide;
s2 preparation of modified bismuth vanadate
Adding the bismuth vanadate containing the silicon dioxide prepared in s13 into a hydrofluoric acid solution, stirring, centrifuging, washing to be neutral, and drying to obtain modified bismuth vanadate powder;
s3 preparation of copper/modified bismuth vanadate
S31, dispersing the modified bismuth vanadate powder prepared in the S2 in distilled water, performing ultrasonic treatment, and continuously dropwise adding a copper nitrate solution in the stirring process to obtain a first mixed solution; mixing the first mixtureDrying the solution to obtain Cu2+Modified BiVO4；
s32, the Cu prepared in step s312+Modified BiVO4Adding NaBH4Stirring the solution at a high speed to obtain a particle mixture; and filtering the particle mixture, washing the particle mixture to be neutral by using distilled water, and finally drying to obtain the copper/modified bismuth vanadate.
In the preparation method of the copper/modified bismuth vanadate composite photocatalytic material, preferably, the preparation step of the silica in the step s13 is as follows:
dissolving tetraethyl orthosilicate in absolute ethyl alcohol to obtain tetraethyl orthosilicate solution;
and quickly adding the tetraethyl orthosilicate solution into ammonia water, stirring, reacting to obtain a silicon dioxide mixed solution, centrifuging, washing and drying the silicon dioxide mixed solution to obtain the silicon dioxide.
In the preparation method of the copper/modified bismuth vanadate composite photocatalytic material, preferably, the bismuth source is Bi (NO)3)3·5H2O, the vanadium source is NH4VO3。
In the preparation method of the copper/modified bismuth vanadate composite photocatalytic material, preferably, the molar ratio of the bismuth source to the vanadium source is 1: 1.
In the preparation method of the copper/modified bismuth vanadate composite photocatalytic material, preferably, in step s13, the silica and the BiVO are used4In a molar ratio of (0.5-2.5): 1;
preferably, the silica and the BiVO4In a molar ratio of 2: 1.
In the above preparation method of the copper/modified bismuth vanadate composite photocatalytic material, preferably, the high-temperature calcination in the step s13 is specifically to perform a first heat preservation treatment after heating from room temperature to 280-470 ℃, and then continue to heat to 430-470 ℃ and perform a second heat preservation treatment;
preferably, the first heat preservation treatment time is 1-3h, and the second heat preservation treatment time is 3-5 h.
In the preparation method of the copper/modified bismuth vanadate composite photocatalytic material, preferably, the molar ratio of the silicon dioxide in the step S13 to the hydrofluoric acid in the step S2 is 1: 4.
In the preparation method of the copper/modified bismuth vanadate composite photocatalytic material, preferably, the concentration of the copper nitrate solution in the step s31 is 0.04-2 mol/L;
preferably, the mass ratio of the copper nitrate to the modified bismuth vanadate is (0.02-0.14): 1.
a copper/modified bismuth vanadate composite photocatalytic material prepared by the preparation method.
The application of the copper/modified bismuth vanadate composite photocatalytic material prepared by the preparation method of the copper/modified bismuth vanadate composite photocatalytic material is to photocatalytic degradation of organic pollutants.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
the invention adopts SiO2For BiVO4Modifying to prepare the modified BiVO with uniformly dispersed particle size4The micro-nano particles are loaded with nano-particle copper on the basis, so that the photocatalytic performance of the composite photocatalytic material is effectively improved; the composite photocatalytic material prepared by the invention uses Cu to replace gold and silver, and utilizes the plasma resonance effect of Cu to further increase the absorption of visible light, accelerate the separation of electron hole pairs and the migration efficiency to the surface of the catalyst, and improve the photocatalytic activity4Under the irradiation of visible light, the performance of photocatalytic degradation of organic pollutants is greatly improved.
In the invention, Cu nano particles are loaded on the modified BiVO4For unmodified BiVO4The amount of Cu nano particles which can be loaded is less than 5 percent, and the modified BiVO4The loading capacity can reach about 10 percent, and the modified BiVO4BiVO (BiVO) with smaller particle size and rougher surface and modified Cu nanoparticles4Better uniformity of upper load and junctionThe resultant strength is higher; fully utilizes the excellent characteristics of the Cu nano particles and effectively promotes BiVO4The photocatalytic performance of (a).
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is a scanning electron micrograph of a modified bismuth vanadate prepared in example 1 of the present invention;
FIG. 2 shows BiVO of examples 1, 6, 7 and 8 of composite photocatalytic materials of the present invention and comparative example 14XRD test pattern of (a);
FIG. 3 shows BiVO of examples 1, 6, 7 and 8 of composite photocatalytic materials of the present invention and comparative example 14Ultraviolet-visible absorption spectrum test contrast chart of (1);
FIG. 4 shows BiVO of examples 1, 6, 7 and 8 of composite photocatalytic materials of the present invention and comparative example 14A comparison graph of fluorescence spectrum test of (1);
FIG. 5 is an enlarged comparative graph of fluorescence spectrum tests of the composite photocatalytic materials of examples 1, 6, 7 and 8 in FIG. 4;
FIG. 6 is a comparison graph of the photocatalytic materials of examples 1, 6, 7 and 8 of the present invention and comparative examples 1 and 2 applied to photocatalytic degradation of rhodamine B.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The preparation method of the copper/modified bismuth vanadate composite photocatalytic material mainly comprises three stepsFirstly, preparing bismuth vanadate containing silicon dioxide, preparing for preparing modified bismuth vanadate with a rough surface in the subsequent step, adding a solution containing a bismuth source into a solution containing a vanadium source, preparing a bismuth vanadate solution in an acidic environment, soaking silicon dioxide powder into the bismuth vanadate solution, and calcining the obtained mixture at a high temperature to obtain the bismuth vanadate containing the silicon dioxide; then adding bismuth vanadate containing silicon dioxide into a hydrofluoric acid solution, and preparing modified bismuth vanadate with a rough surface by utilizing the corrosion of hydrofluoric acid on the silicon dioxide; finally, the modified bismuth vanadate is put into water, copper ion solution is dripped in the high-speed stirring process, copper ions are loaded on the surface of the modified bismuth vanadate, and then the copper ions are reduced by a reducing agent to prepare Cu/modified BiVO4A composite photocatalytic material.
The invention provides a preparation method of a copper/modified bismuth vanadate composite photocatalytic material, which comprises the following steps:
s1 preparation of bismuth vanadate containing silicon dioxide
s11, dissolving a bismuth source in an organic solvent, and stirring to obtain a solution A;
s12, mixing a vanadium source, ascorbic acid, a nitric acid solution and distilled water in a container, heating and cooling to room temperature to obtain a solution B;
s13, adding the solution A into the solution B under stirring, and obtaining BiVO after reaction4Solution, then soaking the silicon dioxide powder in BiVO4Obtaining a mixture in the solution; calcining the mixture at high temperature to obtain bismuth vanadate containing silicon dioxide;
in a specific embodiment of the invention, the bismuth source is Bi (NO)3)3·5H2O, the vanadium source is NH4VO3；
In a specific embodiment of the invention, the molar ratio of the bismuth source to the vanadium source is 1: 1.
In one embodiment of the present invention, the silicon dioxide and BiVO in step s134In a molar ratio of (0.5-2.5): 1 (e.g., 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4: 1); preference is given toGround, silica and BiVO4In a molar ratio of 2: 1.
In an embodiment of the present invention, the preparation step of the silica in step s13 is:
dissolving tetraethyl orthosilicate in absolute ethyl alcohol to obtain tetraethyl orthosilicate solution;
and quickly adding the tetraethyl orthosilicate solution into ammonia water, stirring, reacting to obtain a silicon dioxide mixed solution, centrifuging, washing and drying the silicon dioxide mixed solution to obtain silicon dioxide powder. In the embodiment of the present invention, the high-temperature calcination in step s13 is specifically performed by performing a first heat-preservation treatment after raising the temperature from room temperature to 280-; preferably, the first heat preservation treatment time is 1-3h (such as 1.2h, 1.4h, 1.6h, 1.8h, 2.0h, 2.2h, 2.4h, 2.6h, 2.8h and 3.0h), and the second heat preservation treatment time is 3-5h (such as 3.2h, 3.4h, 3.6h, 3.8h, 4.0h, 4.2h, 4.4h, 4.6h, 4.8h and 5.0 h); preferably, the rate of temperature rise is 1 deg.C/min.
S2 preparation of modified bismuth vanadate
Adding the bismuth vanadate containing silicon dioxide prepared in s13 into a hydrofluoric acid solution, stirring, centrifuging, washing to be neutral, and drying to obtain modified bismuth vanadate powder;
in one embodiment of the present invention, the molar ratio of silicon dioxide in step S13 to hydrofluoric acid in step S2 is 1: 4.
Preferably, the modified bismuth vanadate powder is small particles with the particle size of 80-150 nm.
S3 preparation of copper/modified bismuth vanadate
S31, dispersing the modified bismuth vanadate powder prepared in the step S2 into distilled water, firstly performing ultrasonic treatment, and then continuously dropwise adding a copper nitrate solution in the high-speed stirring process to obtain a first mixed solution; drying the first mixed solution to obtain Cu2+Modified BiVO4；
s32 Cu prepared in step s312+Modified BiVO4Adding NaBH4Stirring the solution at a high speed to obtain a particle mixture; the particle mixture was filtered and washed with distilled water to neutrality and finally dried to obtain copper/modified bismuth vanadate.
In a specific embodiment of the present invention, the concentration of the copper nitrate solution in step s31 is 0.04-2mol/L (e.g., 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.10mol/L, 0.15mol/L, 0.20mol/L, 0.25mol/L, 0.30mol/L, 0.35mol/L, 0.40mol/L, 0.45mol/L, 0.50mol/L, 0.55mol/L, 0.60mol/L, 0.65mol/L, 0.70mol/L, 0.75mol/L, 0.8mol/L, 0.85mol/L, 0.90mol/L, 1.00mol/L, 1.10mol/L, 1.20mol/L, 1.30mol/L, 1.40mol/L, 1.50mol/L, 1.90mol/L, 1.80mol/L, 1.60 mol/L);
preferably, the mass ratio of the copper nitrate to the modified bismuth vanadate is (0.02-0.14): 1 (e.g., 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.11:1, 0.12:1, 0.13: 1).
In the embodiment of the invention, 2%, 6%, 10% and 14% of Cu/modified BiVO4Namely, the mass ratios of copper nitrate to modified bismuth vanadate are respectively 0.02, 0.06, 0.1 and 0.14.
Preferably, the stirring speed of the high-speed stirring in the step s31 is 600-1000 rpm (such as 700 rpm, 800 rpm, 900 rpm).
The copper/modified bismuth vanadate composite photocatalytic material prepared by the invention is used for photocatalytic degradation of organic pollutants.
The preparation method uses the following raw materials: bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O), ammonium metavanadate (NH)4VO3) Ascorbic acid (C)6H8O6) Silicon dioxide (SiO)2) Copper nitrate (Cu (NO)3)2·H2O), sodium borohydride (NaBH)4) Distilled water (H)2O), ethylene glycol (C)2O2H6) Methanol (CH)3OH), nitric acid (HNO)3) Hydrofluoric acid (HF), practice of the inventionThe chemical reagents used in the examples were all of analytical purity.
Example 1
The preparation method of the copper/modified bismuth vanadate composite photocatalytic material provided by the embodiment comprises the following steps:
s1 preparation of bismuth vanadate containing silicon dioxide
1.6169g (3.33mmol) of bismuth nitrate pentahydrate is dissolved in a mixed solution of 1ml of glycol and 2ml of methanol, and a transparent mixed solution A is obtained after stirring for 1 hour; wherein methanol is used as solvent, and glycol is used as reducing agent and cosolvent.
0.3899g (3.33mmol) of ammonium metavanadate, 0.5871g (3.33mmol) of ascorbic acid, 0.33mL of a 68 wt% nitric acid solution and 2mL of distilled water were mixed in a 50mL beaker, heated to 70 ℃, and then cooled to room temperature to obtain a dark green mixed aqueous solution B;
adding the solution A into the solution B under stirring, and stirring, mixing and reacting for 1h to obtain a bismuth vanadate solution;
0.4005g of silicon dioxide (molar ratio of silicon dioxide to bismuth vanadate is 2: 1) are soaked in a bismuth vanadate solution for 3h, then the mixture is calcined at high temperature in a muffle furnace, from room temperature to 300 ℃ at a heating rate of 1 ℃/min, and is kept at 300 ℃ for 2h, and then heating is continued from 300 ℃ to 450 ℃ at a heating rate of 1 ℃/min, and is kept at the temperature for 4h, thereby producing the bismuth vanadate containing silicon dioxide.
S2 preparation of modified bismuth vanadate
Preparing a hydrofluoric acid solution (26.64mmol), and mixing 1.16ml of hydrofluoric acid with the volume concentration fraction of 40% and 6.96ml of distilled water in a plastic beaker to prepare the hydrofluoric acid solution; adding the bismuth vanadate containing silicon dioxide prepared in the step S1 into the bismuth vanadate, stirring for 2h, and removing the silicon dioxide;
and centrifuging the precipitate, washing the precipitate to be neutral by distilled water, and drying the precipitate for 12 hours at the temperature of 60 ℃ to obtain the modified bismuth vanadate with the rough surface structure.
FIG. 1 shows a scanning electron microscope image of the modified bismuth vanadate prepared according to the embodiment of the invention.
S3 preparation of copper/modified bismuth vanadate
0.2g (0.617mmol) of modified bismuth vanadate is weighed, dissolved in 40ml of distilled water and subjected to ultrasonic treatment for 30min, and then magnetic stirring is carried out for 1 h;
continuously dropwise adding 1.6ml of copper nitrate with the concentration of 0.1966mol/l in high-speed stirring of 600-charge 1000 r/min, wherein the mass ratio of the copper nitrate to the modified bismuth vanadate is 0.1, the dropwise adding time is 2min, continuously stirring for 1h, and drying the mixed solution at 80 ℃ for 12h to obtain Cu2+Modified BiVO4；
0.02g of NaBH4Adding into 5ml distilled water to obtain solution, and adding into Cu2+Modified BiVO4In the middle, stirring vigorously for 15 minutes; filtering the obtained product, washing the product with distilled water for 2-3 times, and finally drying the product at 60 ℃ for 12 hours to obtain Cu/modified BiVO4。
Wherein, the preparation process of the silicon dioxide used in S1 is as follows:
preparing tetraethyl orthosilicate solution: uniformly mixing 4.5mL of tetraethyl orthosilicate (TEOS) with 45.5mL of ethanol to obtain tetraethyl orthosilicate solution;
preparing ammonia water: adding l6.25ml ethanol and 24.5ml distilled water into 9ml of concentrated ammonia water, placing the mixture in a flask, and magnetically stirring to obtain an ammonia water solution;
quickly adding tetraethyl orthosilicate solution into ammonia water, avoiding the tetraethyl orthosilicate solution from contacting with the wall of a bottle, reducing the stirring speed after 1min, sealing the mouth of the bottle by using a paraffin sealing film, and continuously reacting for 2 h; and finally, centrifuging the mixed solution, washing for 3 times by using ethanol, and drying to obtain silicon dioxide powder.
The purpose of avoiding the tetraethyl orthosilicate solution from contacting the bottle wall is to avoid the reaction of the tetraethyl orthosilicate solution with water or uncleaned impurities on the wall of the cup, reduce the loss of tetraethyl orthosilicate and make the generated silicon dioxide more uniform.
Photocatalytic degradation test
The copper/modified bismuth vanadate prepared in the embodiment is used for photocatalytic degradation of rhodamine B, and the catalytic activity of the rhodamine B is verified.
100mg of the catalyst copper/modified bismuth vanadate solution prepared in the embodiment and 100ml of rhodamine B (10mg/L) solution are taken as degradation objects. Before illumination, the catalyst is put into rhodamine B solution and stirred for 30min in a dark place, after adsorption and desorption balance is achieved, a light source is turned on, illumination is carried out under magnetic stirring, samples are taken every 10min, and supernatant liquid is taken for testing after centrifugation. And testing the solution after reaching the adsorption and desorption balance for a degradation rate within 70min as a performance test data result. The degradation rate of the catalyst prepared in the embodiment in 70min for photocatalytic degradation of rhodamine B is shown in Table 1 below.
Example 2
The difference between this example and example 1 is that: the amount of silica in step S1 was changed to 0.1001g (molar ratio of silica to bismuth vanadate was 0.5:1), and the volume of hydrofluoric acid was 0.29ml and the volume of distilled water was 1.74ml when hydrofluoric acid solution was prepared in step S2, and the other method steps were the same as in example 1 and will not be described again.
The copper/modified bismuth vanadate prepared in the embodiment is used for photocatalytic degradation of rhodamine B, the catalytic activity of the copper/modified bismuth vanadate is verified, and the obtained catalytic performance is shown in table 1 below.
Example 3
The difference between this example and example 1 is that: changing the amount of the silicon dioxide in the step S1 to 0.2003g (the molar ratio of the silicon dioxide to the bismuth vanadate is 1:1), and taking 0.58ml of hydrofluoric acid and 3.48ml of distilled water when preparing the hydrofluoric acid solution in the step S2; calcining at the high temperature of step S1 from room temperature to 280 ℃ at the heating rate of 1 ℃/min, preserving the heat at 280 ℃ for 2 hours, then continuously heating at the heating rate of 1 ℃/min from 280 ℃ to 460 ℃, and keeping the temperature for 4 hours, thereby generating the bismuth vanadate containing silicon dioxide; other method steps are the same as embodiment 1 and are not described herein again.
The copper/modified bismuth vanadate prepared in the embodiment is used for photocatalytic degradation of rhodamine B, the catalytic activity of the copper/modified bismuth vanadate is verified, and the obtained catalytic performance is shown in table 1 below.
Example 4
The difference between this example and example 1 is that: changing the amount of the silica in the step S1 to 0.3004g (the molar ratio of the silica to the bismuth vanadate is 1.5:1), and taking 0.87ml of hydrofluoric acid and 5.22ml of distilled water when preparing the hydrofluoric acid solution in the step S2; calcining at the high temperature of step S1 from room temperature to 290 ℃ at the heating rate of 1 ℃/min, preserving the heat at 280 ℃ for 2.5 hours, then continuously heating at the heating rate of 1 ℃/min from 290 ℃ to 460 ℃, and keeping the temperature for 3.5 hours, thereby generating the bismuth vanadate containing silicon dioxide; other method steps are the same as embodiment 1 and are not described herein again.
The copper/modified bismuth vanadate prepared in the embodiment is used for photocatalytic degradation of rhodamine B, the catalytic activity of the copper/modified bismuth vanadate is verified, and the obtained catalytic performance is shown in table 1 below.
Example 5
The difference between this example and example 1 is that: changing the amount of silicon dioxide in step S1 to 0.5007g (the molar ratio of silicon dioxide to bismuth vanadate is 2.5:1), and taking 1.45ml of hydrofluoric acid and 8.7ml of distilled water when preparing the hydrofluoric acid solution in step S2; calcining at the high temperature of step S1 from room temperature to 310 ℃ at the heating rate of 1 ℃/min, preserving the heat at 310 ℃ for 3 hours, then continuously heating at the heating rate of 1 ℃/min from 310 ℃ to 440 ℃, and keeping the temperature for 4.5 hours, thereby generating the bismuth vanadate containing silicon dioxide; other method steps are the same as embodiment 1 and are not described herein again.
The copper/modified bismuth vanadate prepared in the embodiment is used for photocatalytic degradation of rhodamine B, the catalytic activity of the rhodamine B is verified, and the obtained catalytic performance is shown in the following table 1.
Example 6
The difference between this example and example 1 is that: when copper nitrate is added dropwise in step S3, the amount of copper nitrate is changed such that the mass ratio of copper nitrate to modified bismuth vanadate is 2%, and the other method steps are the same as those in example 1 and are not described herein again.
The copper/modified bismuth vanadate prepared in the embodiment is used for photocatalytic degradation of rhodamine B, the catalytic activity of the copper/modified bismuth vanadate is verified, and the obtained catalytic performance is shown in table 1 below.
Example 7
The difference between this example and example 1 is that: when copper nitrate is added dropwise in step S3, the amount of copper nitrate is changed such that the mass ratio of copper nitrate to modified bismuth vanadate is 6%, and the other method steps are the same as those in example 1 and are not described herein again.
The copper/modified bismuth vanadate prepared in the embodiment is used for photocatalytic degradation of rhodamine B, the catalytic activity of the copper/modified bismuth vanadate is verified, and the obtained catalytic performance is shown in table 1 below.
Example 8
The difference between this example and example 1 is that: when copper nitrate is added dropwise in step S3, the amount of copper nitrate is changed such that the mass ratio of copper nitrate to modified bismuth vanadate is 14%, and the other method steps are the same as those in example 1 and are not described herein again.
The copper/modified bismuth vanadate prepared in the embodiment is used for photocatalytic degradation of rhodamine B, the catalytic activity of the copper/modified bismuth vanadate is verified, and the obtained catalytic performance is shown in table 1 below.
Comparative example 1
The comparative example differs from example 1 in that: in step S1, no silica is added to modify bismuth vanadate, the prepared bismuth vanadate solution is directly calcined at high temperature to obtain bismuth vanadate, and the photocatalytic performance of the bismuth vanadate is tested, and other method steps are the same as those in embodiment 1 and are not described herein again.
The bismuth vanadate prepared in the comparative example was used for photocatalytic degradation of rhodamine B, the catalytic activity thereof was verified, and the obtained catalytic performance was shown in table 1 below.
Comparative example 2
The comparative example differs from example 1 in that: in step S1, the bismuth vanadate is modified without adding silica, but the surface of the bismuth vanadate is also loaded with the nano-copper particles, and other steps are the same as those in embodiment 1 and are not described herein again.
The copper/bismuth vanadate prepared in the comparative example was used for photocatalytic degradation of rhodamine B, the catalytic activity thereof was verified, and the obtained catalytic performance was shown in table 1 below.
Comparative example 3
The comparative example differs from example 1 in that: the amount of silica in step S1 was changed to 0.05g (the molar ratio of silica to bismuth vanadate was 0.25:1), and the hydrofluoric acid solution prepared in step S2 had a volume of 0.145ml of hydrofluoric acid and a volume of 0.87ml of distilled water, and the other steps were the same as in example 1 and will not be described again.
The copper/modified bismuth vanadate prepared in the comparative example was used for photocatalytic degradation of rhodamine B, the catalytic activity thereof was verified, and the obtained catalytic performance was shown in table 1 below.
Comparative example 4
The comparative example differs from example 1 in that: the amount of silica in step S1 was changed to 0.6009g (the molar ratio of silica to bismuth vanadate was 3:1), and the volume of hydrofluoric acid was 1.74ml and the volume of distilled water was 10.44ml when the hydrofluoric acid solution was prepared in step S2, and the other steps were the same as in example 1 and will not be described again.
The copper/modified bismuth vanadate prepared in the comparative example was used for photocatalytic degradation of rhodamine B, the catalytic activity thereof was verified, and the obtained catalytic performance was shown in table 1 below.
TABLE 1 degradation rate of composite photocatalytic materials prepared in examples and comparative examples
The copper/modified bismuth vanadate prepared in the embodiments 1 to 8 of the invention has a remarkable effect when being applied to photocatalytic degradation of rhodamine B, and the degradation rate reaches 99.7% at most in 70min, while compared with the simple bismuth vanadate prepared in the comparative example 1 and the copper/bismuth vanadate composite photocatalytic material prepared in the comparative example 2 without modification, the copper/modified bismuth vanadate composite photocatalytic material prepared in the embodiments of the invention has greatly improved photocatalytic degradation performance.
FIGS. 2 and 3 show examples 1, 6, 7 and 8 of composite photocatalytic materials of the present invention and BiVO of comparative example 14An XRD test pattern and an ultraviolet-visible absorption spectrum test contrast diagram are obtained; as can be seen from the figure: BiVO modified along with Cu nano particles4The phenomenon that the diffraction angle position of the characteristic diffraction peak of the BiVO gradually moves to the right due to the increase of the upper loading amount shows that the BiVO is modified by the Cu load4When the interplanar spacing is reduced, for example, the diffraction angle of the main diffraction peak of the main crystal plane is changed as follows: pure phase BiVO4The diffraction angle at the (121) plane is 28.8897 DEG, and the diffraction angle is minimal; 2% Cu/modified BiVO4The diffraction angle of (a) is 28.9048 °; 6% Cu/modified BiVO4Has a diffraction angle of 28.9098 °; 10% Cu/modified BiVO4Has a diffraction angle of 28.9179 °; 14% Cu/modified BiVO4Has a diffraction angle of 28.9567 °; furthermore, the intensity of the diffraction of the crystal planes changes, pure BiVO4The diffraction intensity at (121) plane is 13920, which is the smallest value; and 2% Cu/modified BiVO4Has a diffraction intensity of 20437; 6% Cu/modified BiVO420635; 10% Cu/modified BiVO4The diffraction intensity of (a) reaches a maximum of 21697; and 14% Cu/modified BiVO4The diffraction intensity of (2) was 18100, and a drop occurred. This indicates that 10% Cu loading is an optimum loading. The ultraviolet-visible absorption spectrum (fig. 3) shows that when the loading amount is 10% of Cu, the Cu/modified BiVO4 has the highest absorbance in the visible light region, which also shows the best photocatalytic effect.
In general, the fluorescence spectrum PL of a semiconductor material is widely used as an effective technique for the migration, transfer, and recombination processes of photo-generated electron-hole pairs excited under light irradiation. Lower PL intensity generally indicates higher efficiency of photo-induced electron hole separation and thus higher photocatalytic performance. BiVO prepared under 370nm excitation is shown in FIGS. 4 and 54And Cu/modified BiVO4All samples had prominent PL peaks with 10% Cu/modified BiVO4The fluorescence spectrum intensity of the sample is the lowest, which shows that the composite catalyst in the embodiment has the best photocatalysis effect.
Fig. 6 is a comparison graph of the photocatalytic materials of examples 1, 6, 7, and 8 and comparative examples 1 and 2 of the present invention applied to photocatalytic degradation of rhodamine B, and when the mass ratio of copper to modified bismuth vanadate is 0.1, i.e., the loading amount is 10% Cu, the prepared composite catalytic material has the strongest light absorption capacity and the best catalytic effect within the same time.
In summary, the following steps: the invention adopts SiO2For BiVO4Modifying to prepare BiVO with uniformly dispersed particle size4The micro-nano particles are loaded with nano-particle copper on the basis, so that the photocatalytic performance of the composite photocatalytic material is effectively improved; composite photocatalysis prepared by the inventionThe material uses Cu to replace gold and silver, and utilizes the plasma resonance effect of Cu to further increase the absorption of visible light, accelerate the separation of electron hole pairs and improve the photocatalytic activity4Under the irradiation of visible light, the performance of photocatalytic degradation of organic pollutants is greatly improved.
The modified bismuth vanadate has small particle size and BiVO4The surface is rougher, and Cu can be better and uniformly loaded on BiVO4And the dispersion is better, and the bonding strength is higher. Loading Cu nano particles on BiVO4For unmodified BiVO4The amount of Cu nano particles which can be loaded is less than 5 percent, and the modified BiVO4The loading capacity can reach about 10 percent; fully utilizes the excellent characteristics of the Cu nano particles and effectively promotes BiVO4The photocatalytic performance of (a).
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a copper/modified bismuth vanadate composite photocatalytic material is characterized by comprising the following steps:
s1 preparation of bismuth vanadate containing silicon dioxide
s11, dissolving a bismuth source in an organic solvent, and stirring to obtain a solution A;
s12, mixing a vanadium source, ascorbic acid, a nitric acid solution and distilled water in a container, heating and cooling to room temperature to obtain a solution B;
s13, adding the solution A into the solution B under the stirring condition, and obtaining BiVO after reaction4Solution, then soaking silica in said BiVO4Obtaining a mixture in the solution; calcining the mixture at high temperature to obtain bismuth vanadate containing silicon dioxide; the silica and the BiVO4In a molar ratio of (0.5-2.5):1; the high-temperature calcination is specifically to carry out first heat preservation treatment after the temperature is raised from room temperature to 280-470 ℃, and then to carry out second heat preservation treatment after the temperature is raised to 430-470 ℃;
s2 preparation of modified bismuth vanadate
Adding the bismuth vanadate containing the silicon dioxide prepared in s13 into a hydrofluoric acid solution, stirring, centrifuging, washing to be neutral, and drying to obtain modified bismuth vanadate powder; the particle size of the modified bismuth vanadate powder is 80-150 nm;
s3 preparation of copper/modified bismuth vanadate
S31, dispersing the modified bismuth vanadate powder prepared in the S2 in distilled water, performing ultrasonic treatment, and continuously dropwise adding a copper nitrate solution in the stirring process to obtain a first mixed solution; drying the first mixed solution to obtain Cu2+Modified BiVO4(ii) a The concentration of the copper nitrate solution is 0.04-2 mol/L; the mass ratio of the copper nitrate to the modified bismuth vanadate is (0.02-0.14): 1;
s32, the Cu prepared in step s312+Modified BiVO4Adding NaBH4Stirring the solution at a high speed to obtain a particle mixture; filtering the particle mixture, washing the particle mixture to be neutral by using distilled water, and finally drying to obtain copper/modified bismuth vanadate;
the preparation steps of the silicon dioxide in the step s13 are as follows:
dissolving tetraethyl orthosilicate in absolute ethyl alcohol to obtain tetraethyl orthosilicate solution;
and quickly adding the tetraethyl orthosilicate solution into ammonia water, stirring, reacting to obtain a silicon dioxide mixed solution, centrifuging, washing and drying the silicon dioxide mixed solution to obtain the silicon dioxide.
2. The method for preparing the copper/modified bismuth vanadate composite photocatalytic material according to claim 1, wherein the bismuth source is Bi (NO)3)3·5H2O, the vanadium source is NH4VO3。
3. The method for preparing the copper/modified bismuth vanadate composite photocatalytic material as claimed in claim 2, wherein the molar ratio of the bismuth source to the vanadium source is 1: 1.
4. The method for preparing the copper/modified bismuth vanadate composite photocatalytic material according to claim 1, wherein the silica and the BiVO are prepared4In a molar ratio of 2: 1.
5. The method for preparing the copper/modified bismuth vanadate composite photocatalytic material as claimed in claim 1, wherein the first heat preservation treatment time is 1-3 hours, and the second heat preservation treatment time is 3-5 hours.
6. The method for preparing the copper/modified bismuth vanadate composite photocatalytic material as recited in claim 1, wherein the molar ratio of the silicon dioxide in the step S13 to the hydrofluoric acid in the step S2 is 1: 4.
7. The copper/modified bismuth vanadate composite photocatalytic material prepared by the preparation method of the copper/modified bismuth vanadate composite photocatalytic material as claimed in any one of claims 1 to 6.
8. An application of the copper/modified bismuth vanadate composite photocatalytic material prepared by the preparation method of the copper/modified bismuth vanadate composite photocatalytic material according to any one of claims 1 to 6, wherein the copper/modified bismuth vanadate composite photocatalytic material is applied to photocatalytic degradation of organic pollutants.
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